US2786732A - Process for raising the melting point of poly-e-caprolactam filaments, threads, and yarns by treatment with gaseous formaldehyde and products produced thereby - Google Patents

Process for raising the melting point of poly-e-caprolactam filaments, threads, and yarns by treatment with gaseous formaldehyde and products produced thereby Download PDF

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Publication number
US2786732A
US2786732A US340051A US34005153A US2786732A US 2786732 A US2786732 A US 2786732A US 340051 A US340051 A US 340051A US 34005153 A US34005153 A US 34005153A US 2786732 A US2786732 A US 2786732A
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United States
Prior art keywords
threads
yarns
filaments
caprolactam
treatment
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Expired - Lifetime
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US340051A
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English (en)
Inventor
Gabler Rudolf
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Inventa AG fuer Forschung und Patentverwertung
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Inventa AG fuer Forschung und Patentverwertung
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/21—Nylon

Definitions

  • This invention relates to the production of products with high melting points from polyamides. More par ticularly, the invention relates to a process for improving the properties of shaped articles prepared from e-caprolactam. Among these shaped articles are threads and yarns for general use, and cord as well as cord fabrics for tires.
  • This application is a continuation-in-part to the co-pending applications Ser. Nos. 176,052 and 176,053 both filed July 26, 1950, now abandoned.
  • the reduction in strength is probably due to the looseningo'f-the structure by the soaking means and, furthermore, the space required by the methylol groups formed in the first reaction step has alooseni'ng efiect and a partial demolition of the polyamide chains finally seems to take place in the acid medium.
  • Patent F Certain disadvantageous properties of polyamide fabrics, which are hardly disturbing in other applications, as for example the always present plastic stretch, a certain thermoplasticity at temperatures such as occur in highly stressed tires, as well as their low afiinity for rubber or rubber-like coverings hitherto still stood in the way of general use of polyamide cord fabrics.
  • the inventor has discovered that the above-mentioned disadvantages of the formaldehyding and other treatments used hitherto can be completely avoided if the products undergoing the treatment are first subjected to a cold drawing operation and thereafter treated with gaseous formaldehyde in the absence of all means adapted to dissolve or soak the treated material. Since the formation of methylol bridges takes place with simultaneous removal of water, this reaction is accelerated when working in the absence of water. Obviously, the acceleration is so effective that the intermediary alkylol stage is of short duration and the formation of methylol bridges is achieved under essential maintenance of the original crystalline structure.
  • the materials to be treated are only subjected to a cold-drawing process, i. e. a drawing process occurring-at room temperature, in a single stage.
  • a cold-drawing process i. e. a drawing process occurring-at room temperature
  • the cold-drawing operation brings about an increase in the length of the fibers by about 250-400%; hot-drawing at temperatures of about 180 C. effects a further increase in length of 2050%.
  • the drawing operation may be carried out in any known manner.
  • the yarns may, e. g. be wound onto perforated metal cylinders, while being drawn. If a twisting operation is to be combined with the drawing operation, i. e. if thread formation is intended, the fibers are rewound from bobbins onto perforated metal cylinders, the tensioning force on the thread being at least 1 gram/ den.
  • the threads are wound with a large angle of crossing, e. g. an angle of 3045. This is done for the purpose of making the inner layers of thread easily accessible to the agents with which they are subsequently treated; the washing liquids during the cleansing stage, dry .air during the drying step, and vapors of aldehyde during the aldehyde operation.
  • the three operations could also be carried out subsequently in the same apparatus (see drawing).
  • the temperature range for the subsequent formaldehyding with gaseous formaldehyde lies between and 180 C., preferably at C. I may proceed by letting the formaldehyde vapors, which are developed from paraformaldehyde or some other material furnishing formaldehyde, react with the polyamide by means of a heated inert gas, for example nitrogen.
  • the reaction may be considerably accelerated by the use of pressure, but may also be carried out at atmospheric pressure.
  • Poly-e-caprolactam synthetic linear polyamide filaments, threads, and yarns produced by subjecting said filaments, threads and yarns to a cold-drawing process, whereby they are extended to from 350%-400% of their original length, then drying the same to free them completely from water, and thereafter reacting them with dry gaseous formaldehyde, at a temperature ranging from l20 to 180 C. in an environment free from catalysts and substantially consisting of an inert gas for a period of several hours, said treated material having a weight increase, as compared to the starting material, of from 8- 14%, and a melting point raised by from to C.
  • a cord fabric for vehicle and airplane tires made of poly-e-caprolactam synthetic linear polyamide fibers produced by subjecting said polyamides to a cold-drawing process whereby they are extended to 350%-400% of their original length, dried, and thereafter reacted with dry gaseous formaldehyde, at a temperature ranging from 120 to 180 C. in an environment free from catalysts and substantially consisting of an inert gas for a period of several hours and having as a result of said reaction a weight increase, as compared to the starting material, of about 8-14% and a melting point increased by 80-150" C. 5.
  • the process of improving poly-e-caprolactam synthetic linear polyamide fibers to be made into cord fabric which comprises cold-drawing said fibers to from 350% to 400% of their original length, drying the same to free them completely from water, and thereafter reacting them with dry gaseous formaldehyde, at a temperature ranging from 120 to 180 C. in an environment free from catalysts and substantially consisting of an inert gas for a period of several hours until the weight of the treated material has increased by about 8-15 6.
  • the process of improving poly-e-caprolactam synthetic linear polyamide fibers to be made into cord fabric which comprises subjecting said fibers to a colddrawing operation at room temperature until an extension of the fiber length of about 250400% has been reached, then subjecting the fibers to a hotdrawing operation at a temperature of about -190 C. until a further extension of the fibers of about 20 to 50% is obtained, drying the same to free them completely from water, and thereafter reacting them with dry gaseous formaldehyde, at a temperature ranging from 120 to C. in an environment free from catalysts and substantially consisting of an inert gas for a period of several hours until the weight of the treated material has increased by about 8-15%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
US340051A 1949-08-20 1953-03-03 Process for raising the melting point of poly-e-caprolactam filaments, threads, and yarns by treatment with gaseous formaldehyde and products produced thereby Expired - Lifetime US2786732A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH698337X 1949-08-20

Publications (1)

Publication Number Publication Date
US2786732A true US2786732A (en) 1957-03-26

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US340051A Expired - Lifetime US2786732A (en) 1949-08-20 1953-03-03 Process for raising the melting point of poly-e-caprolactam filaments, threads, and yarns by treatment with gaseous formaldehyde and products produced thereby

Country Status (5)

Country Link
US (1) US2786732A (nl)
BE (1) BE496475A (nl)
FR (1) FR1055771A (nl)
GB (1) GB698337A (nl)
NL (1) NL75527C (nl)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3094718A (en) * 1960-03-09 1963-06-25 Rohm & Haas Process of treating filaments and yarns of thermoplastic addition polymers
US3303169A (en) * 1962-01-18 1967-02-07 Du Pont High-modulus, high-tenacity, lowshrinkage polyamide yarn
US3486839A (en) * 1965-10-14 1969-12-30 Soo Valley Co Production of nylon fiber of improved heat resistance

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB582520A (en) * 1944-08-15 1946-11-19 John Richard Lewis Modification of the properties of filaments, films and other shaped articles derived from nylon
US2430953A (en) * 1945-02-20 1947-11-18 Du Pont Process for improving the properties of polyamide fibers
US2434247A (en) * 1944-08-15 1948-01-13 Ici Ltd Production of elastic nylon articles
US2516562A (en) * 1946-12-03 1950-07-25 Du Pont Process of making artificial wool from nylon fibers
US2540726A (en) * 1946-12-03 1951-02-06 Du Pont Treatment of a heat set, oriented nylon fabric with formaldehyde

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB582520A (en) * 1944-08-15 1946-11-19 John Richard Lewis Modification of the properties of filaments, films and other shaped articles derived from nylon
US2434247A (en) * 1944-08-15 1948-01-13 Ici Ltd Production of elastic nylon articles
US2430953A (en) * 1945-02-20 1947-11-18 Du Pont Process for improving the properties of polyamide fibers
US2516562A (en) * 1946-12-03 1950-07-25 Du Pont Process of making artificial wool from nylon fibers
US2540726A (en) * 1946-12-03 1951-02-06 Du Pont Treatment of a heat set, oriented nylon fabric with formaldehyde

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3094718A (en) * 1960-03-09 1963-06-25 Rohm & Haas Process of treating filaments and yarns of thermoplastic addition polymers
US3303169A (en) * 1962-01-18 1967-02-07 Du Pont High-modulus, high-tenacity, lowshrinkage polyamide yarn
US3486839A (en) * 1965-10-14 1969-12-30 Soo Valley Co Production of nylon fiber of improved heat resistance

Also Published As

Publication number Publication date
BE496475A (nl)
NL75527C (nl)
GB698337A (en) 1953-10-14
FR1055771A (fr) 1954-02-22

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